Stepwise construction of manganese-chromium carbonyl chalcogenide complexes: Synthesis, electrochemical properties, and computational studies

Minghuey Shieh; Chia Yeh Miu; Kuo Chih Huang; Chung Feng Lee; Bao Gun Chen

doi:10.1021/ic200885h

Stepwise construction of manganese-chromium carbonyl chalcogenide complexes: Synthesis, electrochemical properties, and computational studies

Minghuey Shieh^*, Chia Yeh Miu, Kuo Chih Huang, Chung Feng Lee, Bao Gun Chen

^*此作品的通信作者

化學系

研究成果: 雜誌貢獻 › 期刊論文 › 同行評審

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摘要

When trigonal-bipyramidal clusters, [PPN][E₂Mn ₃(CO)₉] (E = S, Se), were treated with Cr(CO)₆ and PPNCl in a molar ratio of 1:1:2 or 1:2:2 in 4 M KOH/MeCN/MeOH solutions, mono-Cr(CO)₅-incorporated HE₂Mn₃-complexes [PPN]₂[HE₂Mn₃Cr(CO)₁₄] (E = S, [PPN]₂[1a]; Se, [PPN]₂[1b]), respectively, were formed. X-ray crystallographic analysis showed that 1a and 1b were isostructural and each displayed an E₂Mn₃ square-pyramidal core with one of the two basal E atoms externally coordinated with one Cr(CO)₅ group and one Mn-Mn bond bridged by one hydrogen atom. However, when the TMBA ⁺ salts for [E₂Mn₃(CO)₉]^- were mixed with Cr(CO)₆ in a molar ratio of 1:1 in 4 M KOH/MeOH solutions and refluxed at 60 °C, mono-Cr(CO)₃-incorporated E ₂Mn₃Cr octahedral clusters [TMBA]₃[E ₂Mn₃Cr(CO)₁₂] (E = S, [TMBA]₃[2a]; Se, [TMBA]₃[2b]), respectively, were obtained. Clusters 2a and 2b were isostructural, and each consisted of an octahedral E₂Mn ₃Cr core, in which each Mn-Mn or Mn-Cr bond of the Mn₃Cr plane was semibridged by one carbonyl ligand. Clusters 1a and 1b (with [TMBA] salts) underwent metal core closure to form octahedral clusters 2a and 2b upon treatment with KOH/MeOH at 60 °C. In addition, 1a and 1b were found to undergo cluster expansion to form di-Cr(CO)₅-incorporated HE ₂Mn₃-clusters [HE₂Mn₃Cr ₂(CO)₁₉]^2- (E = S, 3a; Se, 3b), respectively, upon the addition of 1 or 2 equiv of Cr(CO)₆ heated in refluxing CH₂Cl₂. Clusters 3a and 3b were structurally related to clusters 1a and 1b, but with the other bare E atom (E = S, 3a; Se, 3b) further externally coordinated with one Cr(CO)₅ group. The nature, cluster transformation, and electrochemical properties of the mixed manganese-chromium carbonyl sulfides and selenides were systematically discussed in terms of the chalcogen elements, the introduced chromium carbonyl group, and the metal skeleton with the aid of molecular calculations at the BP86 level of the density functional theory.

原文	英語
頁（從 - 到）	7735-7748
頁數	14
期刊	Inorganic Chemistry
卷	50
發行號	16
DOIs	https://doi.org/10.1021/ic200885h
出版狀態	已發佈 - 2011 8月 15

ASJC Scopus subject areas

物理與理論化學
無機化學

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10.1021/ic200885h

其它文件與鏈接

CCDC 844221: Experimental Crystal Structure Determination
Shieh, M. (Creator), Miu, C.-Y. (Creator), Huang, K.-C. (Creator), Lee, C.-F. (Creator) & Chen, B.-G. (Creator), Unknown Publisher, 2011
DOI: 10.5517/ccxbgym, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccxbgym&sid=DataCite
資料集: Dataset
CCDC 844222: Experimental Crystal Structure Determination
Shieh, M. (Creator), Miu, C.-Y. (Creator), Huang, K.-C. (Creator), Lee, C.-F. (Creator) & Chen, B.-G. (Creator), Unknown Publisher, 2011
DOI: 10.5517/ccxbgzn, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccxbgzn&sid=DataCite
資料集: Dataset
CCDC 844224: Experimental Crystal Structure Determination
Shieh, M. (Creator), Miu, C.-Y. (Creator), Huang, K.-C. (Creator), Lee, C.-F. (Creator) & Chen, B.-G. (Creator), Unknown Publisher, 2011
DOI: 10.5517/ccxbh1r, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccxbh1r&sid=DataCite
資料集: Dataset

引用此

@article{14573f3c0f934288adb80a8985f8dc02,

title = "Stepwise construction of manganese-chromium carbonyl chalcogenide complexes: Synthesis, electrochemical properties, and computational studies",

abstract = "When trigonal-bipyramidal clusters, [PPN][E2Mn 3(CO)9] (E = S, Se), were treated with Cr(CO)6 and PPNCl in a molar ratio of 1:1:2 or 1:2:2 in 4 M KOH/MeCN/MeOH solutions, mono-Cr(CO)5-incorporated HE2Mn3-complexes [PPN]2[HE2Mn3Cr(CO)14] (E = S, [PPN]2[1a]; Se, [PPN]2[1b]), respectively, were formed. X-ray crystallographic analysis showed that 1a and 1b were isostructural and each displayed an E2Mn3 square-pyramidal core with one of the two basal E atoms externally coordinated with one Cr(CO)5 group and one Mn-Mn bond bridged by one hydrogen atom. However, when the TMBA + salts for [E2Mn3(CO)9]- were mixed with Cr(CO)6 in a molar ratio of 1:1 in 4 M KOH/MeOH solutions and refluxed at 60 °C, mono-Cr(CO)3-incorporated E 2Mn3Cr octahedral clusters [TMBA]3[E 2Mn3Cr(CO)12] (E = S, [TMBA]3[2a]; Se, [TMBA]3[2b]), respectively, were obtained. Clusters 2a and 2b were isostructural, and each consisted of an octahedral E2Mn 3Cr core, in which each Mn-Mn or Mn-Cr bond of the Mn3Cr plane was semibridged by one carbonyl ligand. Clusters 1a and 1b (with [TMBA] salts) underwent metal core closure to form octahedral clusters 2a and 2b upon treatment with KOH/MeOH at 60 °C. In addition, 1a and 1b were found to undergo cluster expansion to form di-Cr(CO)5-incorporated HE 2Mn3-clusters [HE2Mn3Cr 2(CO)19]2- (E = S, 3a; Se, 3b), respectively, upon the addition of 1 or 2 equiv of Cr(CO)6 heated in refluxing CH2Cl2. Clusters 3a and 3b were structurally related to clusters 1a and 1b, but with the other bare E atom (E = S, 3a; Se, 3b) further externally coordinated with one Cr(CO)5 group. The nature, cluster transformation, and electrochemical properties of the mixed manganese-chromium carbonyl sulfides and selenides were systematically discussed in terms of the chalcogen elements, the introduced chromium carbonyl group, and the metal skeleton with the aid of molecular calculations at the BP86 level of the density functional theory.",

author = "Minghuey Shieh and Miu, {Chia Yeh} and Huang, {Kuo Chih} and Lee, {Chung Feng} and Chen, {Bao Gun}",

year = "2011",

month = aug,

day = "15",

doi = "10.1021/ic200885h",

language = "English",

volume = "50",

pages = "7735--7748",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "16",

}

TY - JOUR

T1 - Stepwise construction of manganese-chromium carbonyl chalcogenide complexes

T2 - Synthesis, electrochemical properties, and computational studies

AU - Shieh, Minghuey

AU - Miu, Chia Yeh

AU - Huang, Kuo Chih

AU - Lee, Chung Feng

AU - Chen, Bao Gun

PY - 2011/8/15

Y1 - 2011/8/15

N2 - When trigonal-bipyramidal clusters, [PPN][E2Mn 3(CO)9] (E = S, Se), were treated with Cr(CO)6 and PPNCl in a molar ratio of 1:1:2 or 1:2:2 in 4 M KOH/MeCN/MeOH solutions, mono-Cr(CO)5-incorporated HE2Mn3-complexes [PPN]2[HE2Mn3Cr(CO)14] (E = S, [PPN]2[1a]; Se, [PPN]2[1b]), respectively, were formed. X-ray crystallographic analysis showed that 1a and 1b were isostructural and each displayed an E2Mn3 square-pyramidal core with one of the two basal E atoms externally coordinated with one Cr(CO)5 group and one Mn-Mn bond bridged by one hydrogen atom. However, when the TMBA + salts for [E2Mn3(CO)9]- were mixed with Cr(CO)6 in a molar ratio of 1:1 in 4 M KOH/MeOH solutions and refluxed at 60 °C, mono-Cr(CO)3-incorporated E 2Mn3Cr octahedral clusters [TMBA]3[E 2Mn3Cr(CO)12] (E = S, [TMBA]3[2a]; Se, [TMBA]3[2b]), respectively, were obtained. Clusters 2a and 2b were isostructural, and each consisted of an octahedral E2Mn 3Cr core, in which each Mn-Mn or Mn-Cr bond of the Mn3Cr plane was semibridged by one carbonyl ligand. Clusters 1a and 1b (with [TMBA] salts) underwent metal core closure to form octahedral clusters 2a and 2b upon treatment with KOH/MeOH at 60 °C. In addition, 1a and 1b were found to undergo cluster expansion to form di-Cr(CO)5-incorporated HE 2Mn3-clusters [HE2Mn3Cr 2(CO)19]2- (E = S, 3a; Se, 3b), respectively, upon the addition of 1 or 2 equiv of Cr(CO)6 heated in refluxing CH2Cl2. Clusters 3a and 3b were structurally related to clusters 1a and 1b, but with the other bare E atom (E = S, 3a; Se, 3b) further externally coordinated with one Cr(CO)5 group. The nature, cluster transformation, and electrochemical properties of the mixed manganese-chromium carbonyl sulfides and selenides were systematically discussed in terms of the chalcogen elements, the introduced chromium carbonyl group, and the metal skeleton with the aid of molecular calculations at the BP86 level of the density functional theory.

AB - When trigonal-bipyramidal clusters, [PPN][E2Mn 3(CO)9] (E = S, Se), were treated with Cr(CO)6 and PPNCl in a molar ratio of 1:1:2 or 1:2:2 in 4 M KOH/MeCN/MeOH solutions, mono-Cr(CO)5-incorporated HE2Mn3-complexes [PPN]2[HE2Mn3Cr(CO)14] (E = S, [PPN]2[1a]; Se, [PPN]2[1b]), respectively, were formed. X-ray crystallographic analysis showed that 1a and 1b were isostructural and each displayed an E2Mn3 square-pyramidal core with one of the two basal E atoms externally coordinated with one Cr(CO)5 group and one Mn-Mn bond bridged by one hydrogen atom. However, when the TMBA + salts for [E2Mn3(CO)9]- were mixed with Cr(CO)6 in a molar ratio of 1:1 in 4 M KOH/MeOH solutions and refluxed at 60 °C, mono-Cr(CO)3-incorporated E 2Mn3Cr octahedral clusters [TMBA]3[E 2Mn3Cr(CO)12] (E = S, [TMBA]3[2a]; Se, [TMBA]3[2b]), respectively, were obtained. Clusters 2a and 2b were isostructural, and each consisted of an octahedral E2Mn 3Cr core, in which each Mn-Mn or Mn-Cr bond of the Mn3Cr plane was semibridged by one carbonyl ligand. Clusters 1a and 1b (with [TMBA] salts) underwent metal core closure to form octahedral clusters 2a and 2b upon treatment with KOH/MeOH at 60 °C. In addition, 1a and 1b were found to undergo cluster expansion to form di-Cr(CO)5-incorporated HE 2Mn3-clusters [HE2Mn3Cr 2(CO)19]2- (E = S, 3a; Se, 3b), respectively, upon the addition of 1 or 2 equiv of Cr(CO)6 heated in refluxing CH2Cl2. Clusters 3a and 3b were structurally related to clusters 1a and 1b, but with the other bare E atom (E = S, 3a; Se, 3b) further externally coordinated with one Cr(CO)5 group. The nature, cluster transformation, and electrochemical properties of the mixed manganese-chromium carbonyl sulfides and selenides were systematically discussed in terms of the chalcogen elements, the introduced chromium carbonyl group, and the metal skeleton with the aid of molecular calculations at the BP86 level of the density functional theory.

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JO - Inorganic Chemistry

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ER -

Stepwise construction of manganese-chromium carbonyl chalcogenide complexes: Synthesis, electrochemical properties, and computational studies

摘要

ASJC Scopus subject areas

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資料集

CCDC 844221: Experimental Crystal Structure Determination

CCDC 844222: Experimental Crystal Structure Determination

CCDC 844224: Experimental Crystal Structure Determination

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